Water repelling article

ABSTRACT

Disclosed herein is a water repelling article for use in clothing comprising, at least one inner material and at least one outer material that substantially covers the inner material, wherein the article further comprises at least one water repelling agent uniformly distributed throughout the article and the article has a resiliently deformable non-flat three dimensional shape. In addition, a process for forming a water repelling article for use in clothing is disclosed.

TECHNICAL FIELD

The present invention relates to a water repelling article and a processfor forming the same.

BACKGROUND

The listing or discussion of an apparently prior-published document inthis specification should not necessarily be taken as an acknowledgementthat the document is part of the state of the art or is common generalknowledge.

The field of highly functionalised textiles is a growing market for manygarment related industries. One of the most important properties fortextiles, and one that demands a high value, is the ability to repelwater. This ability to repel water is generally achieved by subjecting atextile to chemical treatment before further processing steps such ascolouring, cutting, shaping, forming and sewing etc. The conventionalmethods used to perform this chemical treatment normally include a stepof wetting the textile with a water repelling chemical before performingdrying and curing steps.

The water repelling chemicals used to treat textiles to provide waterrepelling properties work by chemically modifying the surface of thetextiles, such that water is at least partially repelled by thechemically modified textile.

While standard techniques used to provide textiles and articles ofclothing with water repellent properties are able to provide areasonable level of water repellence, there are still major problemsassociated such standard techniques, especially when treating non-flatarticles. These problems include an uneven distribution of chemicalacross the textiles/articles and the deformation of non-flat articles.This can lead to an inconsistent water repelling performance from thefinal products.

Accordingly, there remains a need for improved articles (and thereforeprocesses) with improved water repellence properties.

SUMMARY OF INVENTION

In a first aspect of the invention, there is provided a water repellingarticle for use in clothing comprising at least one inner material andat least one outer material that substantially covers the innermaterial, wherein the article further comprises at least one waterrepelling agent uniformly distributed throughout the article and thearticle has a resiliently deformable non-flat three dimensional shape.

In embodiments of the invention, the at least one outer material maycompletely cover the inner material.

In further embodiments of the invention, the article:

-   -   (a) may have a curvilinear topography. For example, the article        may be shaped like a cup; and/or    -   (b) may form part of a shoe, medical equipment (e.g. a casting        liner inner), or, more particularly, a bra, a brassiere,        swimwear, sportswear or casual wear; and/or    -   (c) may be one where at least part of the article has a fixed        three-dimensional shape that is complementary in shape to one of        the group consisting of hands, arms, and, more particularly, the        head, shoulders, buttocks, breasts, knees, elbows and feet.

In further embodiments of the invention, the article may have animproved texture in a blind test compared to a water repelling articleprepared in a process comprising the step of immersing said article intoa water-repellant precursor solution.

In yet further embodiments of the invention, the at least one waterrepelling agent may have been impregnated within the article followingplasma activation of said article to provide an improved feel andappearance. For example, the at least one water repelling agent maycomprise paraffin waxes, silicones, silanes, fluorinated polymers,non-fluorinated water repelling polymers or a combination thereof, orthe water repelling agent comprises fluorine and carbon atoms. Aparticular example of the water repelling agent comprises fluoroacrylatepolymer.

In still further embodiments of the invention, the at least one innermaterial may be an open or closed-cell foam.

In embodiments of the invention, the at least one outer material may bea fabric. For example the fabric is laminated.

In a second aspect of the invention, there is disclosed a processcomprising the steps of:

-   -   (a) providing a starting article comprising at least one inner        material and at least one outer material that substantially        covers the inner material;    -   (b) treating a starting article with at least one water        repelling agent precursor to form a treated article; and    -   (c) curing the treated article to generate the water repelling        agent and form the water repelling article, wherein the starting        article has a resiliently deformable, non-flat three-dimensional        shape.

In an embodiment of the invention, treating the starting article maycomprise immersing the starting article in the at least one waterrepelling agent precursor. For example, the at least one water repellingagent precursor comprises paraffin waxes, silicones, silanes,fluorinated polymers, non-fluorinated water repelling polymers or acombination thereof, or the water repelling agent comprises fluorine andcarbon atoms. A particular example of the water repelling agentprecursor is at least one fluoroacrylate polymer.

In further embodiments of the invention, a step of removing excess waterrepelling agent precursor is performed before curing the treatedarticle. For example, the step of removing excess water repelling agentcomprises feeding the treated article through a roller and/or subjectingthe treated article to centrifugation to provide an extracted article.Optionally, the extracted article may be sprayed with the at least onewater repelling agent precursor.

In certain embodiments of the invention, the treatment step comprises anactivating step, where the starting article is treated with anactivating plasma to generate an activated article and a coating step,where the activated article is treated with an inert plasma and the atleast one water repelling agent precursor (e.g. a water repelling agentprecursor disclosed hereinbefore) to generate the treated article.

In embodiments of the invention, the activating plasma is generated:

-   -   (a) from argon or, more particularly, nitrogen or oxygen gas;        and/or    -   (b) under a reduced pressure (e.g. from 0.1 to 0.5 mbar, such as        from 0.12 to 0.45 mbar, or, more particularly, from 0.2 to 0.5        mbar) and using a power of from 200 W to 300 W (e.g. 250 W) or        under a reduced pressure (e.g. from 0.2 to 0.5 mbar and using a        power of from 150 W to 200 W (e.g. 170 W).

In certain embodiments of the invention, the flow rate of the gas isfrom 10 to 80 sccm (e.g. 60 sccm).

In still further embodiments of the invention, a drying step isperformed before curing the treated article.

In certain embodiments of the invention, the at least one waterrepelling agent precursor in step (b) further comprises at least onewetting agent.

In further embodiments of the invention, the curing in step (c)comprises infrared curing and/or microwave curing.

In yet further embodiments of the invention, the article is as describedin the first aspect of the invention.

Further Aspects and embodiments of the invention are provided in thefollowing numbered clauses.

1. A water repelling article for use in clothing comprising:

-   -   at least one inner material; and    -   at least one outer material that substantially covers the inner        material,    -   wherein the article:        -   further comprises at least one water repelling agent            uniformly distributed throughout the article; and        -   the article has a resiliently deformable non-flat three            dimensional shape.

2. The article according to Clause 1, wherein the at least one outermaterial completely covers the inner material.

3. The article according to Clause 1 or Clause 2, wherein the articlehas a curvilinear topography.

4. The article according to Clauses 1 to 3, wherein the article has acup shape.

5. The article of any one of Clauses 1 to 4, wherein the article formspart of a shoe, medical equipment (e.g. a casting liner inner), or, moreparticularly, a bra, a brassiere, swimwear, sportswear or casual wear.

6. The article of any one of the preceding clauses, wherein at leastpart of the article has a fixed three-dimensional shape that iscomplementary in shape to one of the group consisting of hands, arms,and, more particularly, the head, shoulders, buttocks, breasts, knees,elbows and feet.

7. The article of any one of the preceding clauses, wherein the articlehas an improved texture in a blind test compared to a water repellingarticle prepared in a process comprising the step of immersing saidarticle into a water-repellant precursor solution.

8. The article of any one of the preceding clauses, wherein the at leastone water repelling agent has been impregnated within the articlefollowing plasma activation of said article to provide an improved feeland appearance.

9. The article according to any one of the preceding clauses, whereinthe at least one inner material is an open or closed-cell foam.

10. The article according to any one of the preceding clauses, whereinthe at least one outer material is a fabric.

11. The article according to Clause 10, wherein the fabric is alaminated fabric.

12. The article according to any one of the preceding clauses, whereinthe at least one water repelling agent comprises paraffin waxes,silicones, silanes, fluorinated polymers, non-fluorinated waterrepelling polymers or a combination thereof, or the water repellingagent comprises fluorine and carbon atoms.

13. The article according to Clause 12, wherein the water repellingagent is at least one fluoroacrylate polymer.

14. A process for forming a water repelling article for use in clothing,the process comprising the steps of:

-   -   a) providing a starting article comprising at least one inner        material and at least one outer material that substantially        covers the inner material;    -   b) treating a starting article with at least one water repelling        agent precursor to form a treated article; and    -   c) curing the treated article to generate the water repelling        agent and form the water repelling article, wherein    -   the starting article has a resiliently deformable, non-flat        three-dimensional shape.

15. The process according to Clause 14, wherein treating the startingarticle comprises immersing the starting article in the at least onewater repelling agent precursor.

16. The process according to Clause 15, wherein a step of removingexcess water repelling agent precursor is performed before curing thetreated article.

17. The process according to Clause 16, wherein removing excess waterrepelling agent precursor comprises feeding the treated article througha roller and/or subjecting the treated article to centrifugation toprovide an extracted article.

18. The process according to Clause 17, wherein the extracted article issprayed with the at least one water repelling agent precursor.

19. The process according to Clause 14, wherein the treatment stepcomprises an activating step, where the starting article is treated withan activating plasma to generate an activated article and a coatingstep, where the activated article is treated with an inert plasma andthe at least one water repelling agent precursor to generate the treatedarticle.

20. The process according to Clause 19, wherein the activating plasma isgenerated from nitrogen or oxygen gas, optionally wherein the flow rateof the gas is from 10 to 80 sccm (e.g. 60 sccm).

21. The process according to Clause 19 or Clause 20, wherein theactivating plasma is generated under a reduced pressure and using apower of from 200 W to 300 W.

22. The process according to Clause 21, wherein the reduced pressure isfrom 0.1 to 0.5 mbar (e.g. such as from 0.12 to 0.45 mbar or, moreparticularly, from 0.2 to 0.5 mbar).

23. The process according to Clause 21 or Clause 22, wherein the poweris 250 W.

24. The process according to any one of Clauses 19 to 23, wherein theinert plasma is generated from argon gas, optionally wherein the flowrate of the gas is from 10 to 80 sccm (e.g. 60 sccm).

25. The process according to one of Clauses 19 to 24, wherein the inertplasma is generated under a reduced pressure and using a power of from150 W to 200 W.

26. The process according to Clause 25, wherein the reduced pressure isfrom 0.2 to 0.5 mbar (e.g. such as from 0.12 to 0.45 mbar or, moreparticularly, from 0.2 to 0.5 mbar).

27. The process according to Clause 25 or Clause 26, wherein the poweris 170 W.

28. The process according to any one of Clauses 14 to 27, wherein adrying step is performed before curing the treated article.

29. The process according to any one of clauses 14 to 28, wherein the atleast one water repelling agent precursor comprises paraffin waxes,silicones, silanes, fluorinated polymers, non-fluorinated waterrepelling polymers or a combination thereof, or the water repellingagent comprises fluorine and carbon atoms.

30. The process according to Clause 29, wherein the at least one waterrepelling agent precursor is at least one fluoroacrylate polymer

31. The process according to any one of Clauses 14 to 30, wherein the atleast one water repelling agent precursor in step (b) further comprisesat least one wetting agent.

32. The process according to any one of Clauses 14 to 31, wherein thearticle has a curvilinear topography.

33. The process according to any one of Clauses 14 to 32, wherein thearticle has a cup shape.

34. The process according to any one of Clauses 14 to 33, wherein theprocess further comprises the step of forming a garment that comprisessaid article.

35. The process according to Clause 34, wherein the garment is a shoe,medical equipment (e.g. a casting liner inner), or, more particularly, abra, a brassiere, swimwear, sportswear or casual wear.

36. The process according to any one of Clauses 14 to 35, wherein thecuring in step c) comprises infrared curing and/or microwave curing.

37. The process according to any one of Clauses 14 to 36, wherein the atleast one outer material completely covers the inner material.

38. The process according to any one of Clauses 14 to 37, wherein atleast part of the starting article has a fixed three-dimensional shapethat is complementary in shape to one of the group consisting of hands,arms, or, more particularly, the head, shoulders, buttocks, breasts,knees, elbows and feet.

BRIEF DESCRIPTION OF FIGURES

Aspects and embodiments will be described with reference to thefollowing figures, wherein:

FIG. 1 illustrates a padding roller for extracting water repellent agentprecursor from a treated article.

FIG. 2A illustrates a front view, side view and cross-sectional view ofa bra cup.

FIG. 2B illustrates a cross-sectional view of the bra cup before andafter treatment.

FIG. 3 illustrates the water repelling performance of an untreatedspecimen, a plasma treated specimen and a chemical treated specimen.

FIG. 4 shows an article made according to the current invention andillustrates sections used to test the water repellence of the article.

FIG. 5 depicts the contact angle of the inner and outer layers of thearticle depicted in FIG. 4.

DETAILED DESCRIPTION

Surprisingly, it has been found that an article with improved waterrepellence can be produced by a modified process wherein a non-flat,multi-layered article is subjected to a water repellent treatment.

Thus, there is provided a water repelling article for use in clothingthat comprises at least one inner material and at least one outermaterial that substantially covers the inner material, wherein thearticle further comprises at least one water repelling agent uniformlydistributed throughout the article and the article has a good recoveryat a low force range, is resiliently deformable and has a non-flat threedimensional shape.

The articles described above may be provided by a process comprising thesteps of:

-   -   a) providing a starting article comprising at least one inner        material and at least one outer material that substantially        covers the inner material;    -   b) treating the starting article with at least one water        repelling agent precursor to form a treated article; and    -   c) curing the treated article to generate the water repelling        agent and form the water repelling article, wherein    -   the starting article has a resiliently deformable, non-flat        three dimensional shape.

As used herein, the term, “resiliently deformable non-flat threedimensional shape” refers to an object that has a definedthree-dimensional shape that can be deformed by the application ofpressure and/or force onto said object, but which will return to thedefined shape once said pressure and/or force is removed from theobject. When the pressure and/or force applied onto said object is lessthan or equal to 570 newton (N) the object may return to its definedshape once the pressure or force is removed. Where the pressure and/orforce applied onto said object exceeds 570 N, the object may not returnto its defined shape once the pressure or force is removed, that is, theobject will remain permanently deformed. Any suitable non-flat threedimensional shape that is suitable for use in clothing may be used. Forexample, the shape may have a curvilinear topography 130, as illustratedby the bra cup 100 in FIG. 2A. Alternatively or additionally, thedefined shape may be a shape that is complimentary to the contours ofpart of a body (such as one of the group consisting of hands, arms, ormore particularly, the head, shoulders, buttocks, breasts, knees, elbowsand feet). Thus, the defined three-dimensional shape may be a cup (e.g.complementary in shape to breasts).

As shown in FIG. 2A, the bra cup 100, includes an inner material 110(e.g. foam) and an outer material 120 as a liner. Possible inner andouter materials that may be used for one or more applications are setout hereinbelow. FIG. 2B depicts the inner material 110 and outermaterial before treatment 200 and after treatment 300. As depicted inFIG. 2B, it is believed that the current process and articles contain auniform penetration of chemicals between the layers, which provides theunexpectedly good properties of the garments discussed herein.

The water repelling article of the present invention may be used forclothing. More specifically, the article may form part of a shoe,medical equipment, or, more particularly, a bra, a brassiere, swimwear,sportswear or casual wear.

As an example of medical equipment, the article may be formed into apre-formed casting inner liner. In this example, the inner liner has athree-dimensional shape and is shaped to conform to the surface of thefractured area (and surrounding area covered by the cast), such as along-armed tube for a fracture of the forearm. The pre-formed linerenables perspiration to be channeled away from the skin/cast and helpsto minimise the inconvenience of the subject due to an accumulation ofsweat in the cast.

In certain embodiments of the invention, the shoe may not require thepresence of the inner material. In other embodiments, the shoe requiresthe presence of the inner material.

Alternatively, the article may be used for upholstery. In particular,the article may form part of a textile covering for any one of the groupconsisting of chairs, beds and tables (e.g. a massage table where thewater repelling article forms part of the upholstery of said table).Given the above, the starting article must also be suitable for use inclothing.

When used herein, the term “water repelling article” may be used todescribe the water repellent article comprising at least one inner layerand at least one outer layer. When used herein, it will be understoodthat an “item of clothing” or an “item of upholstery” relates to an itemthat comprises the non-flat three dimensional article mentioned hereinas a component part. Such items may comprise other components that mayalso be water repellent. For example, items of clothing may be selectedfrom the group consisting of a shoe, medical equipment (e.g. a castingliner inner), or, more particularly, a bra, a brassiere, swimwear,sportswear or casual wear, while an item of upholstery may be selectedfrom the group consisting of a covering for a chair, a bed and a table.It will be understood that a “starting article” refers to an object thatmay be used to make the “article” described above and references to“treated article” and “extracted article” should be construedaccordingly. Collectively, the terms, “water repelling article”,“starting article”, “treated article” and “extracted article” may bereferred to herein as an “article”.

The article requires there to be an inner material. This inner materialis responsible for the resiliently deformable, non-flat threedimensional shape of the article. As such any material that can providea resiliently deformable, non-flat three dimensional shape may be usedas the inner material. For example, the inner material may comprise afoam. When the inner material comprises a foam, the foam may be selectedfrom one or more of the group consisting of a closed cell foam, an opencell foam, a reticulated foam and a multilayered foam or combinationsthereof (e.g. the foam may be a foam that has 95% closed cells and 5%open cells, such as a foam with 85% or less closed cells and 15% or moreopen cells). Such foams may be made from, but are not limited to,polyurethane, polyvinyl chloride, polystyrene, natural rubber orsynthetic rubber.

As discussed herein, the inner material is responsible for theresiliently deformable, non-flat three dimensional shape of the article.Thus, in a precursor step to the process disclosed above, there is astep of providing a starting article with the desired non-flat threedimensional shape. This shape may be obtained by any suitable means ofshaping the resiliently deformable material. For example, the shapingmay be accomplished by moulding, pressing, cutting, sanding, sculpting,etching or any suitable combination thereof. The outer material may beattached to the inner material prior to, or after to, the inner materialhas been shaped into the desired non-flat three dimensional shape.

When used herein, the term “substantially covers” may refer to thesituation where the majority of the inner material is covered by theouter material or to a situation where the inner material is entirelycovered by the inner material (i.e. the inner material has no externalfacing surfaces). The outer material may be a single piece material orit may be two or more pieces (e.g., two to ten, four to six or fivepieces) joined together to cover the inner material. When the outermaterial is in two or more pieces, the two or more pieces may be joinedtogether by any means of fastening, for example by stitching, stapling,a fabric hoop and loop fastener, or by the use of an adhesive.

The outer material may be, but is not limited to, a group comprising (orconsisting of) leather, suede leather, composites made using man-made ornatural materials and, more particularly, a fabric material. When theouter material is a fabric material, each piece of fabric material maybe selected from one or more of the group consisting of canvas, and,more particularly, laminated fabrics, microfiber polyester fabrics,nylon fabrics, spandex fabrics and knitted fabrics. For example, theouter material may be a polyester fabric. It will be appreciated thatwhen the material used is a fabric, it may be woven, non-woven orknitted.

The outer material covers the inner material in such a way that theinner material is held within said outer material. This may be by theconformation of the outer material, such that the inner material cannotbe released from the outer material without substantial mechanicaleffort (e.g. where the outer material comprises a first piece and asecond piece, where the first piece is applied to a first face of theinner material and the second piece is applied to the other face of theinner material, where the first piece and second piece of materialoverlap sufficiently that they can be fastened together using stitchesand entirely envelop the inner material).

Alternatively or additionally, the outer material may also be bound tothe inner material by any suitable means of fastening, for example bystitching, stapling, a fabric hoop and loop fastener, or by the use ofan adhesive. In certain embodiments the outer material is bound to theinner material using adhesives.

In order to obtain the desired water repelling properties, a waterrepelling agent is uniformly distributed throughout the article. Whenused herein “uniformly distributed” means that the water repelling agentis evenly distributed across the at least one inner material and the atleast one outer material. Any suitable water repelling agent may beused. Such water repelling agents include paraffin waxes, silicones,silanes, fluorinated polymers, non-fluorinated water repelling polymersor any combination thereof that may be cured or uncured. In particular,the water repelling agent may comprise a fluoroacrylate that hasoptionally been subjected to curing.

It will be appreciated that curing of the water repelling agents willcause a number of chemical changes in said agents. These changes willdepend on the agent itself.

The uniform distribution of the water repelling agent throughout thearticle may help to provide the article with an improved and longerlasting water repelling effect. Without wishing to be bound by theory,it is also speculated that the uniform distribution of the waterrepelling agent throughout the inner and outer layers of the article isresponsible for the particularly good effects demonstrated by thearticle of the current invention, as described in the Examples Sectionbelow.

An article may have an improved texture in a blind test compared to asimilar water repelling article that has been prepared in a processcomprising the step of immersing said article into a water repellingagent precursor solution.

As described herein, “water repelling agent precursor” is a mixturecomprising a water repelling agent component. The water repelling agentprecursor is used to treat a starting article, thus impregnating thewater repelling agent precursor into the starting article, in a uniformdistribution. Following curing of the treated or extracted articlecomprising the water repelling agent precursor, there is formed anarticle with a uniform distribution of water repelling agent throughoutthe outer and inner materials of said article.

The water repelling agent precursor may include any suitable waterrepelling agent component including paraffin waxes, silicones, silanes,fluorinated polymers or any combination thereof. For example, the waterrepelling agent precursor may be a mixture of the water repelling agentcomponent and any suitable solvent. Typical solvents used may includewater and/or acetic acid.

In addition, the water repelling agent precursor may further comprise awetting agent, cross-linking agent, fillers additive, dyeing auxiliary,sizing residue, softening agent, other surface-active compounds or acombination thereof.

In the current process, treating a starting article with a waterrepelling agent precursor may include any suitable method that resultsin the uniform distribution of the water repelling agent precursorthroughout the outer and inner layers of the starting article to form atreated article. For example, such methods may include the applicationof said water repelling agent precursor by immersion treatment or by theapplication of an inert plasma of the water repelling agent to aplasma-activated starting article or combinations thereof.

Treating the starting article with the plasma treatment method disclosedherein improves the feel and appearance of the resulting water repellingarticle compared to a starting article treated using an immersiontreatment method. Without wishing to be bound by theory, the improvedfeel and appearance of the resulting water repelling article may beattributed to the low temperature conditions that can be used in thesubsequent curing step of the plasma-treated article.

When a starting article is subjected to an immersion treatment, it maybe necessary to subject the starting article to a preparation step thatremoves surface impurities. Any suitable method to remove said surfaceimpurities may be used, for example, scouring the starting article orperforming a detergent wash. Without wishing to be bound by theory,removing surface impurities from the starting article may enableefficient penetration of the water repelling agent precursor throughoutthe starting article during treatment.

The starting article may be immersed in the water repelling agentprecursor agent solution for a period of from 10 seconds to 20 minutes,such as 1 minute to 5 minutes. In general, the temperature of the waterrepelling agent precursor solution will be between 10° and 50° C., suchas from 15° to 30° C., e.g. 20° C. The pH of said solution may be from5.0 to 7.0 and the water repelling agent precursor may be present in thewater repelling precursor agent solution in a concentration of from30-50 g/L, optionally, a wetting agent may also be present in thesolution at a concentration of from 1 to 10 mL/L, such as 5 mL/L.

When a starting article undergoes immersion treatment with a waterrepelling agent precursor to form a treated article, an excess of thewater repelling agent precursor may be present when the article isremoved from the immersion (e.g. the excess may be within the outermaterial, inner material and/or on the surface of the treated article).This excess water repelling agent precursor may be extracted using anysuitable method to form an extracted article. The extracted article maybe formed, for example, by feeding the treated article through a paddingroller and/or subjecting the treated article to centrifugation.

In particular, a suitable method of removing excess water repellingagent precursor to form a treated article may include feeding thetreated article between at least one padding roller to extract excesswater repelling agent precursor out from the treated article. Thepadding roller 10 may be a soft rubber padding roller, having a softrubber pad 20 (see FIG. 1). More in particular, the padding roller mayhave an International Rubber Hardness Degree (IRHD) of 45-55. A seriesof padding rollers may be used to optimise the amount of excess waterrepelling agent precursor removed. Alternatively, the treated articlemay be fed through the padding roller multiple times to remove excesswater repelling agent precursor.

Suitable rollers for use in the processes described herein are capableof applying a pressure range from 0.75 to 1.25 bar (0.075 to 0.125 MPa).

The extracted article may have a wet pick-up percentage (%) of 40-90%.In particular the wet pick-up percentage may be 40-65%, 55-70%, 65-90%,50-90%, 80-90%, 40-50%. The wet pick-up percentage of an extractedarticle can be determined using the following equation:

Wet pick-up percentage (%)=((weight of extracted article−weight ofstarting article)/weight of stating article)×100

In certain cases, the extracted article following the removal of theexcess water repelling agent precursor by the means discussed above mayresult in an uneven amount of said agent on the surface of the extractedarticle. In such cases, spray coating of the extracted article with thewater repelling agent precursor may be used to rectify this unevenness.

When plasma treatment is used, the starting article is subjected to alow pressure and temperature plasma treatment, followed by theapplication of an atomised version of the water repelling agentprecursor in a low temperature and low pressure plasma environment.

The plasma treatment first requires that the starting article is placedinto a low pressure environment (e.g. from 0.10 to 0.5 mbar, such asfrom 0.12 to 0.45 mbar, or more particularly, from 0.2 to 0.5 mbar, suchas 0.33 mbar at low temperature (e.g. <100° C.) in a reaction chamber.Subsequently, the starting article is activated by the admission of theprocess gas (e.g. nitrogen or oxygen) into the low-pressure reactionchamber and said gas is subsequently ignited to form a plasma (e.g. bythe application of electrical power of from 180 W to 300 W, such as 200W to 260 W, such as 250 W). The flow rate of the gas may be from 10-80sccm (e.g. from 30 to 70 sccm, such as 60 sccm), for example whenmeasured at 0.3 mbar and 70° C. It will be appreciated by the skilledperson that any suitable flow rate may be used, provided that it enablesthe coating of the article as described herein. As such, it will beappreciated that simple adjustments to the flow rate may be made whenoperating at a different temperature and pressure to ensure that this isaccomplished. The starting article may be treated for at least 5minutes, for example from 7 minutes to 20 minutes, such as 10 minutes)in the plasma. It will be recognised that the plasma formed under suchconditions has a low temperature (e.g. <100° C.). Following theactivation treatment, the plasma gas is evacuated and is replaced by aninert gas (e.g. argon) in the low-pressure reaction chamber, along withan aerosolised form of the water repelling agent precursor (e.g.introduced by the use of an atomiser into said reaction chamber). Theinert gas is ignited to form a plasma (e.g. by the application ofelectrical power of from 100 W to 200 W, such as 125 W to 175 W, such as170 W) and the plasma and water repelling agent precursor are allowed tointeract with the starting article for at least 10 minutes (e.g. from 10minutes to 1 hour, such as 15 minutes to 30 minutes, e.g. 20 minutes).

The weight ratio of the water repelling agent to the inert gas may be4:1 to 1:2, such as 2:1 to 1:1, such as 1.5:1 or 1.46:1.

Where a starting article undergoes plasma treatment, with a waterrepelling agent precursor to form a treated article, removing excesswater repelling agent precursor is generally not necessary.

Following the treatment of the article by immersion and/or plasmatreatment, the article will undergo a drying step. In the case of anarticle that has been subjected to immersion, the drying step willfollow the extraction step (e.g. where the water repelling agentprecursor remains evenly distributed following extraction) or thespraying step (e.g. when the water repelling agent is unevenlydistributed following extraction). While any temperature under thecuring temperature of the water repelling precursor may be used, it ispreferred that the temperature used to dry the treated/extracted articleis under 100° C. For example, the treated or extracted article mayundergo drying at a temperature of 80-100° C. for 20-30 minutes.

While any oven may be used, it is preferred to use a convection-typecuring oven with closed heat elements. This type of heating element mayhelp to prevent yellowing of articles dried therein.

The treated or extracted article must undergo a suitable method ofcuring to provide the water repelling article. Suitable methods ofcuring include heat curing, ultraviolet radiation curing, chemicalcuring, electron beam curing or any combination thereof. Further,examples of heat curing include infrared curing, microwave curing, hotair impingement or any combination thereof.

Heat curing may be performed under any suitable conditions, for example,at a temperature of 110-150° C. In particular, the heat curing may beperformed at a temperature of 110-125° C., 130-145° C., 125-135° C.,115-150° C., 110-145° C., 140-145° C., 140-150° C. Even more inparticular, the heat curing may be carried out at a temperature of110-145° C. In addition, suitable conditions may include heat curing ata temperature as defined above for 2-5 minutes.

In order for curing to occur, the temperature must be at least 110° C.and/or the time greater than or equal to 2 minutes, otherwise thematerial will not have good wash durability. If the curing temperatureis more than 150° C. (e.g. more than 145° C.) and/or the time is greaterthan 5 minutes, then the article may have a harsh hand-feel and maysuffer from yellowing, neither of which are desirable for aestheticreasons.

Upon curing of the treated or extracted article, the impregnated waterrepelling agent precursor undergoes a chemical transformation to providethe water repellent article impregnated with a water repelling agent.Without being bound by theory, this chemical transformation may includecross-linking of the water repelling agent's precursor component polymerchains.

EXPERIMENTAL SECTION Example 1 Immersion Preparation of Water RepellentArticles Example 1a Immersion Preparation of 2D Fabric, Foam Sheet or 3DFoam Cup Water Repellent Articles

A chemical solution containing OLEOPHOBOL™ CP-C fabric protector (adispersion of fluoroacrylate polymers) at a concentration of 40 g/L,PHOBOL™ XAN at a concentration of 5 g/L and INVADINE™ at a concentrationof 5 mL/L was prepared. The chemical solution was maintained at a pH 7(±0.7) by adding acid before being used in a chemical bath. A suitablearticle, in this case a bikini bra cup, was immersed into the chemicalbath for approximately 5 minutes with manual agitation. During thisimmersion step 7%, 1% and 1% of the original amounts of OLEOPHOBOL™PHOBOL™ XAN and INVADINE™ were consumed.

Subsequently, the article was removed from the chemical bath and theexcess chemical solution was removed by extraction. Extraction wasperformed using a padded roller (for example a pad rollerhydro-extractor), having an International Rubber Hardness Degree 50 andat a pressure of 0.1 MPa to provide an extracted article with a wetpick-up percentage of approximately 80%. The extracted article was thensubjected to drying at 100° C. for 25 minutes in a convection oven withcovered heat elements. After cooling, the dried article was thenheat-cured for 5 minutes at 145° C. to provide a water repellentarticle. The resulting water repellent article was then subjected to thewater repelling performance tests as described below.

Example 1b Immersion Preparation of Complex 3D Textile Water RepellentArticles (e.g. High Depth Foam Cup or Finished Garments)

A chemical solution containing OLEOPHOBOL™ CP-C fabric protector (adispersion of fluoroacrylate polymers) at a concentration of 40 g/L,PHOBOL™ XAN at a concentration of 5 g/L and INVADINE™ at a concentrationof 5 mL/L was prepared. The chemical solution was maintained at a pH 7(±0.7) by adding acid before being used in a chemical bath.

A suitable article, in this case a bikini bra cup, was immersed into thechemical bath for approximately 5 minutes with manual agitation. Duringthis immersion step 7%, 1% and 1% of the original amounts of OLEOPHOBOL™PHOBOL™ XAN and INVADINE™ were consumed.

Subsequently, the article was removed from the chemical bath and theexcess chemical solution was removed by extraction. Extraction wasperformed using a centrifuge hydro-extractor (centrifuge diameter ˜800mm) at ˜900 revolutions per minutes (RPM), to provide an extractedarticle with a wet pick-up percentage of approximately 80%. Optionally,additional chemical solution may be applied to selected areas of theextracted article, via chemical spraying, to ensure the evendistribution of the chemical solution across the entire article.

The extracted article was than subjected to drying at 100° C. for 25minutes in a convection oven with covered heat elements. After cooling,the dried article was then heat-cured for 5 minutes at 145° C. toprovide a water repellent article. The resulting water repellent articlewas then subjected to water repelling performance tests as describedbelow.

Example 2 Plasma Preparation of Article

A bikini cup was prepared with a pre-formed foam inner material having85% closed cells and 15% open cells and a fabric covering. Said cup wassubjected to the following treatment steps.

Stage Duration Conditions Vacuuming  5 Min Pressure 0.33 mbar/ Plasmagenerator Power 0 w/No gas Activation 10 Min Pressure 0.33 mbar/ Plasmagenerator Power 250 W/gas used N₂ Coating 20 Min Pressure 0.33 mbar/Plasma generator Power 170 W/gas used Argon

In the coating step, the amount of gas used was 3.57 g, while the waterrepelling agent precursor was present in an amount of 5.36 g in thereaction chamber.

Alternatively, the bikini cup was subjected to the following treatmentsteps.

Stage Duration Conditions Vacuuming 2 Min Pressure 0.33 mbar/ Plasmagenerator Power 0 w/No gas Activation 5 Min Pressure 0.33 mbar/ Plasmagenerator Power 250 W/gas used N₂ Coating 30 Min  Pressure 0.33 mbar/Plasma generator Power 170 W/gas used Argon

The alternative method provided a bikini cup having substantiallyidentical properties.

The flow rate of the gas in the activation and coating steps for theplasma treatments described above was 60 sccm.

Water Repelling Performance Test

A water repelling performance test was performed to assess the waterrepelling performance of an untreated specimen (i.e. a bikini foam cupcovered in fabric that has not been subjected to any treatment), a waterrepelling specimen produced via plasma treatment (i.e. Example 2; plasmaspecimen) and a water repelling specimen produced via immersiontreatment (i.e. Example 1; immersion specimen). The tests were carriedout under the same conditions (i.e. humidity and temperature) and thespecimens were conditioned prior to testing as set out below. The testwas carried out according to following step:

-   -   1. The untreated specimen, and a specimen made according to each        of Example 1 and Example 2 were dried in an air conditioned room        for 1 day at a temperature of 24° C. and relative humidity of        65-67.    -   2. The dry specimens were then weighed.    -   3. The specimens were then dipped into a 15 cm deep water tank        (containing purified water) for 15 minutes. A metal paper weight        was used to ensure that the specimens were fully immersed in the        water.    -   4. Once taken out of the tank the specimens were allowed to drip        for 5 minutes.    -   5. Specimens were then weighed again.    -   6. The specimens were then hung in an air conditioned room at        24° C.    -   7. The weight of the specimens were then measured at 15 minute        intervals.

As illustrated by FIG. 3, the plasma specimen demonstrates a superiorwater repelling performance compared to the immersion specimen (ART asreferred to in FIG. 3), which in turn is superior to an untreatedspecimen.

Contact Angle Test

A cup (outer and inner layer) made using the immersion method (e.g. asdescribed in Example 1 b) was provided. The cup was divided into sixnotional sections, as illustrated by FIG. 4. A water droplet of1/20^(th) of a mL was deposited onto each section and the contact anglewas measured. The outer layer was then stripped off the cup and thecontact angle was measured as described before for water droplets indirect contact with the inner material. The results are summarised inTable 1 and FIG. 5.

Cup Section 1 2 3 4 5 6 Outer Layer 101 112 109 101 113 121 (Degrees)Inner Layer 115 111 111 120 113 118 (Degrees)

As shown in the Table and FIG. 5, the contact angles for the inner andouter layers are greater than 100 and less than 120 degrees. A contactangle of greater than 100 degrees is indicative of good waterrepellency. Therefore, this test demonstrates that the water repellingagent is evenly distributed throughout the inner and outer layers of thecup.

Blind Tests

This test was carried out with the purpose of assessing the change inthe hand feel of a garment after application of a water repellentfinish, either in chemical form or plasma form. One product (a bikinibra) was left untreated, while one product was treated with plasma andanother with wet chemicals. Two sets of samples were prepared in thismanner. Each set including a Regular Garment (untreated), a Plasmatreated Garment and a Chemical treated garment.

The samples were provided to a set of 10 people who were able to providean expert opinion on the hand feel of the garments. This group of peopleconsisted of experts from quality, product development and thelaboratory. The assessors were not informed of the condition of theproducts and were asked to compare the hand feel of treated anduntreated samples blindly in the two sets of samples.

For each product, the hand feel was assessed and rated. They assessorswere asked to rate the hand feel on a scale of 1-5, where 1 is theharshest feel, while 5 is the softest. Table 2 illustrates the resultsobtained from the experts for each product and the summarized hand feelobservation for the two treatment options.

TABLE 2 Assessor Sample Set Regular Plasma Wet  1 (Prod Dev) 1 3 5 1 2 35 1  2 (Quality) 1 5 3 1 2 5 3 1  3 (Quality) 1 1 5 3 2 5 3 1  4(Quality) 1 1 5 3 2 5 3 1  5 (Quality) 1 5 1 3 2 3 1 5  6 (Quality) 1 35 1 2 3 5 1  7 (Lab) 1 5 3 1 2 5 1 3  8 (Lab) 1 5 1 3 2 5 1 3  9 (Lab) 11 5 3 2 3 5 1 10 (Lab) 1 3 5 1 2 5 3 1 Average 3.7 3.4 1.9 StandardDeviation of Sample 1.5 1.7 1.2

The hand-feel of the plasma treated sample is similar to the hand-feelobtained for an untreated sample, while the hand feel for the chemicallyimmersed product is considerably worse than the untreated and plasmatreated samples.

1. A process for forming a water repelling article for use in clothing,the process comprising the steps of: a) providing a starting articlecomprising at least one inner material and at least one outer materialthat substantially covers the inner material; b) treating a startingarticle with at least one water repelling agent precursor to form atreated article; and c) curing the treated article to generate the waterrepelling agent and form the water repelling article, wherein thestarting article has a resiliently deformable, non-flatthree-dimensional shape.
 2. The process according to claim 1, whereinthe treatment step comprises an activating step, where the startingarticle is treated with an activating plasma to generate an activatedarticle and a coating step, where the activated article is treated withan inert plasma and the at least one water repelling agent precursor togenerate the treated article.
 3. The process according to claim 2,wherein the activating plasma is generated from nitrogen or oxygen gas,optionally wherein the flow rate of the gas is from 10 to 80 sccm (e.g.60 sccm).
 4. The process according to claim 2, wherein the activatingplasma is generated under a reduced pressure and using a power of from200 W to 300 W (e.g. the power is 250 W), optionally wherein the reducedpressure is from 0.1 to 0.5 mbar (e.g. such as from 0.2 to 0.5 mbar orfrom 0.12 to 0.45 mbar).
 5. The process according to claim 2, wherein:(a) the inert plasma is generated from argon gas; and/or (b) the inertplasma is generated under a reduced pressure and using a power of from150 W to 200 W (e.g. the power is 170 W), optionally the reducedpressure is from 0.1 to 0.5 mbar (e.g. such as from 0.2 to 0.5 mbar orfrom 0.12 to 0.45 mbar); and/or (c) the flow rate of the gas is from 10to 80 sccm (e.g. 60 sccm).
 6. The process according to claim 1, whereintreating the starting article comprises immersing the starting articlein the at least one water repelling agent precursor.
 7. The processaccording to claim 6, wherein a step of removing excess water repellingagent precursor is performed before curing the treated article. 8-9.(canceled)
 10. The process according to claim 1, wherein the at leastone water repelling agent precursor comprises paraffin waxes, silicones,silanes, fluorinated polymers, non-fluorinated water repelling polymersor a combination thereof, or the water repelling agent comprisesfluorine and carbon atoms, optionally wherein the at least one waterrepelling agent precursor is at least one fluoroacrylate polymer
 11. Theprocess according to claim 1, wherein the at least one water repellingagent precursor in step (b) further comprises at least one wettingagent.
 12. The process according to claim 1, wherein the article has acurvilinear topography, optionally wherein the article has a cup shape.13. The process according to claim 1, wherein the process furthercomprises the step of forming a garment that comprises said article,optionally wherein the garment is a shoe, medical equipment (e.g. acasting liner inner), a bra, a brassiere, swimwear, sportswear or casualwear.
 14. (canceled)
 15. The process according to claim 1, wherein theat least one outer material completely covers the inner material. 16.The process according to claim 1, wherein at least part of the startingarticle has a fixed three-dimensional shape that is complementary inshape to one of the group consisting of hands, arms, the head,shoulders, buttocks, breasts, knees, elbows and feet.
 17. A waterrepelling article for use in clothing comprising: at least one innermaterial; and at least one outer material that substantially covers theinner material, wherein the article: further comprises at least onewater repelling agent uniformly distributed throughout the article; andthe article has a resiliently deformable non-flat three dimensionalshape.
 18. The article according to claim 17, wherein the at least oneouter material completely covers the inner material.
 19. The articleaccording to claim 17, wherein the article has a curvilinear topography,optionally wherein the article has a cup shape.
 20. The article of claim17, wherein: (a) the article forms part of a shoe, medical equipment(e.g. a casting liner inner), a bra, a brassiere, swimwear, sportswearor casual wear; and/or (b) at least part of the article has a fixedthree-dimensional shape that is complementary in shape to one of thegroup consisting of hands, arms, the head, shoulders, buttocks, breasts,knees, elbows and feet.
 21. The article of claim 17, wherein the articlehas an improved texture in a blind test compared to a water repellingarticle prepared in a process comprising the step of immersing saidarticle into a water-repellant precursor solution.
 22. The article ofclaim 17, wherein the at least one water repelling agent has beenimpregnated within the article following plasma activation of saidarticle to provide an improved feel and appearance.
 23. (canceled) 24.The article according to claim 17, wherein the at least one waterrepelling agent comprises paraffin waxes, silicones, silanes,fluorinated polymers, non-fluorinated water repelling polymers or acombination thereof, or the water repelling agent comprises fluorine andcarbon atoms, optionally wherein the water repelling agent is at leastone fluoroacrylate polymer.